Bridging Titanium Nitrido Complexes Containing A Linear Ti-N-Ti Core with A Two-Coordinate Nitrido Ligand.

A series of titanium m2-nitrido complexes supported by the triamidoamine ligand Xy-N3N (Xy-N3N = {(3,5-Me2C6H3)NCH2CH2}3N3-) is reported. The titanium azido complex [(Xy-N3N)TiN3] (1-N3), prepared by salt metathesis of the chloride complex [(Xy-N3N)TiCl] (1-Cl) with NaN3, reacted with lithium metal or with alkali metal naphthalenides (alkali metal M = Na, K, and Rb) in THF to give the corresponding dinuclear m2-nitrido complexes M[(Xy-N3N)Ti=N-Ti(Xy-N3N)] (2-M; M = Li, Na, K, Rb). Single crystal X-ray diffraction studies of 2-Li, 2-Na, and 2-K revealed alkali metal dependent structures in the solid state. While 2-Li and 2-K contain a m2-nitrido ligand with a linear Ti-N-Ti core, 2-Na includes a m3-nitrido ligand as part of a T-shape Ti2NaN fragment with the sodium cation weekly coordinated to the nitrido nitrogen atom. When the synthesis of the nitrido complexes was carried out in the presence of excess alkali metals, selective decomposition of the nitrido complexes was observed affording some intractable titanium species along with the trialkali metal salts [M3(Xy-N3N)] (3-M) (M = Li, Na, K, and Rb). These salts were also prepared by deprotonation of (Xy-N3N)H3 with the corresponding alkali metal hexamethyldisilazide and characterized by multinuclear NMR spectroscopy as well as single crystal X-ray diffraction.

Benzylic C(sp3 )-H Bond Oxidation with Ketone Selectivity by a Cobalt(IV)-Oxo Embedded in a ß-Barrel Protein.

Artificial metalloenzymes have emerged as biohybrid catalysts that allow to combine the reactivity of a metal catalyst with the flexibility of protein scaffolds. This work reports the artificial metalloenzymes based on the ß-barrel protein nitrobindin NB4, in which a cofactor [CoII X(Me3 TACD-Mal)]+ X- (X=Cl, Br; Me3 TACD=N,N' ,N''-trimethyl-1,4,7,10-tetraazacyclododecane, Mal=CH2 CH2 CH2 NC4 H2 O2 ) was covalently anchored via a Michael addition reaction. These biohybrid catalysts showed higher efficiency than the free cobalt complexes for the oxidation of benzylic C(sp3 )-H bonds in aqueous media. Using commercially available oxone (2KHSO5 ⋅ KHSO4 ⋅ K2 SO4 ) as oxidant, a total turnover number of up to 220 and 97 % ketone selectivity were achieved for tetralin. As catalytically active intermediate, a mononuclear terminal cobalt(IV)-oxo species [Co(IV)=O]2+ was generated by reacting the cobalt(II) cofactor with oxone in aqueous solution and characterized by ESI-TOF MS.

Hydrogenolysis of Cationic Half-Sandwich Zinc Complexes Containing a Chelating Amine: Facile Cleavage of Zinc-Carbon Bond by Dihydrogen to Give Zinc Hydride Cations.

Cationic half-sandwich zinc complexes containing chelating amines [Cp*Zn(Ln)][BAr4 F] (2 a, Cp*=η3-C5Me5, Ln=N,N,N',N'-tetramethylethylenediamine, TMEDA; 2 b, Ln=N,N,N',N'-tetraethylethylenediamine, TEEDA; 2 c, Cp*=η1-C5Me5, Ln=N,N,N',N'',N''-pentamethyldiethylenetriamine, PMDTA; Ar4 F=(3,5-(CF3)2C6H3)4) reacted with dihydrogen (ca. 2 bar) in THF at 80 °C to give molecular zinc hydride cations [(Ln)ZnH(thf)m][BAr4 F] (3 a,b, m=1; 3 c, m=0) previously reported along with Cp*H. Pseudo first-order kinetics with respect to the concentration of 2 b suggests heterolytic cleavage of dihydrogen by the Zn-Cp* bond, reminiscent of σ-bond metathesis. Hydrogenolysis of the zinc cation 2 b in the presence of benzophenone gave the zinc alkoxide [(TEEDA)Zn(OCHPh2)(thf)][BAr4 F] (5 b). Cation 2 b was shown to catalytically hydrogenate N-benzylideneaniline. The PMDTA complex 2 c underwent C-H bond activation in acetonitrile to give a dinuclear µ-κC,κN-cyanomethyl zinc complex [(PMDTA)Zn(CH2CN)]2[BAr4 F]2 (6 c).

Dihydrogen Cleavage by a Zinc-Zinc Bond of a Heteroleptic Dizinc(I) Cation.

Oxidative addition of dihydrogen across a metal-metal bond to form reactive metal hydrides in homogeneous catalysis is known for transition metals but not for zinc(I)-zinc(I) bond as found in Carmona's eponymous dizinconene [Zn2Cp*2] (Cp* = η5-C5Me5). Dihydrogen reacted with the heteroleptic zinc(I)-zinc(I) bonded cation [(L2)Zn-ZnCp*][BAr4F] (L2 = TMEDA, N,N,N',N'-tetramethylethylenediamine, TEEDA, N,N,N',N'-tetraethylethylenediamine; ArF = 3,5-(CF3)2C6H3) under 2 bar at 80 °C to give the zinc(II) hydride cation [(L2)ZnH(thf)][BAr4F] along with zinc metal and Cp*H derived from the intermediate [Cp*ZnH]. DFT calculations show that the cleavage of dihydrogen occurs through a highly unsymmetrical transition state. Mechanistic studies agree with a heterolytic cleavage of dihydrogen as a result of the cationic charge and unsymmetrical ligand coordination. To explore the existence of zinc(I) hydride, thermally unstable hydridotriphenylborate complexes of zinc(I) [(L2)Zn(HBPh3)-ZnCp*] (L2 = TMEDA, TEEDA; TMPDA, N,N,N',N'-tetramethyl-1,3-propylenediamine) have been prepared by salt metathesis and were shown to undergo fast exchange with both BPh3 and [HBPh3]-.

Engineered Anchor Peptide LCI with a Cobalt Cofactor Enhances Oxidation Efficiency of Polystyrene Microparticles.

A typical component of polymer waste is polystyrene (PS) used in numerous applications, but degraded only slowly in the environment due to its hydrophobic properties. To increase the reactivity of polystyrene, polar groups need to be introduced. Here, biohybrid catalysts based on the engineered anchor peptide LCI_F16C are presented, which are capable of attaching to polystyrene microparticles and hydroxylating benzylic C-H bonds in polystyrene microparticles using commercially available oxone as oxidant. LCI peptides achieve a dense surface coverage of PS through monolayer formation within minutes in aqueous solutions at ambient temperature. The catalytically active cobalt cofactor Co-L1 or Co-L2 with a modified NNNN macrocyclic TACD ligand (TACD=1,4,7,10-tetraazacyclododecane) is covalently bound to the anchor peptide LCI through a maleimide linker. Compared to the free cofactors, a 12- to 15-fold improvement in catalytic activity using biohybrid catalysts based on LCI_F16C was observed.

Heterobimetallic Hydrides with a Germanium(II)-Zinc Bond.

In the presence of TMEDA (TMEDA=N,N,N',N'-tetramethylethylenediamine), zinc dihydride reacted with germanium(II) compounds (BDI-H)Ge (1) and [(BDI)Ge][B(3,5-(CF3 )2 C6 H3 )4 ] (3) (BDI-H = HC{(C=CH2 )(CMe)(NAr)2 }, BDI = [HC(CMeNAr)2 ]; Ar = 2,6-i Pr2 C6 H3 ) by formal insertion of the germanium(II) center into the Zn-H bond of polymeric [ZnH2 ]n to give neutral and cationic zincagermane with a H-Ge-Zn-H core [(BDI-H)Ge(H)-(H)Zn(tmeda)] (2) and [(BDI)Ge(H)-(H)Zn(tmeda)][B(3,5-(CF3 )2 C6 H3 )4 ] (4), respectively. Compound 2 eliminated [ZnH2 ] giving diamido germylene 1 at 60 °C. Compound 2 and deuterated analogue 2-d2 exchanged with [ZnH2 ]n and [ZnD2 ]n in the presence of TMEDA to give a mixture of 2 and 2-d2 . Compounds 2 and 4 reacted with carbon dioxide (1 bar) at room temperature to form zincagermane diformate [(BDI-H)Ge(OCHO)-(OCHO)Zn(tmeda)] (5) and formate bridged digermylene [({BDI}Ge)2 (µ-OCHO)]+ [B(C6 H3 (CF3 )2 )4 ] (6) along with zinc formate [(tmeda)Zn(µ-OCHO)3 Zn(tmeda)][B(C6 H3 (CF3 )2 )4 ] (7), respectively. The hydridic nature of the Ge-H and Zn-H bonds in 2 and 4 was probed by reactions with Brönsted and Lewis acids.

Strontium Hydride Cations Supported by a Large NNNNN Type Macrocycle: Synthesis, Structure, and Hydrofunctionalization Catalysis.

The use of the 15-membered NNNNN macrocyclic ligand Me5PACP (Me5PACP = 1,4,7,10,13-pentamethyl-1,4,7,10,13-pentaazacyclopentadecane) allowed the isolation of two cationic strontium hydride complexes by hydrogenolysis of benzyl precursors. Treatment of sparingly soluble [(Me5PACP)Sr(CH2Ph)2] with dihydrogen gave free Me5PACP, toluene, and oligomeric strontium hydride [SrH2]n, while hydrogenolysis in the presence of 1 equiv of the benzyl cation [(Me5PACP)Sr(CH2Ph)][B(C6H3-3,5-Me2)4] enabled isolation of the thermally unstable trihydride cation [(Me5PACP)2Sr2(µ-H)3][B(C6H3-3,5-Me2)4]. When the benzyl cation [(Me5PACP)Sr(CH2Ph)][BAr4]2 (Ar = C6H3-3,5-Me2 or C6H4-4-nBu) was reacted with dihydrogen or n-octylsilane, dihydride complexes [(Me5PACP)2Sr2(µ-H)2][BAr4]2 containing a dinuclear core bridged by two hydride ligands were obtained. The soluble dihydride complex [(Me5PACP)2Sr2(µ-H)2][B(C6H4-4-nBu)4]2 was tested in olefin hydrogenation and hydrosilylation catalysis. Kinetic analyses for [(Me5PACP)2Sr2(µ-H)2]2+ showed lower catalytic activity as compared to that of the isostructural calcium homologue [(Me5PACP)2Ca2(µ-H)2]2+. This is explained by a shift in the monomer-dimer equilibrium which precedes the catalytic cycle.

Formation and Reactivity of a Hexahydridosilicate [SiH6 ]2- Coordinated by a Macrocycle-Supported Strontium Cation.

The cationic benzyl complex [(Me4 TACD)Sr(CH2 Ph)][A] (Me4 TACD=1,4,7,10-tetramethyltetraazacyclododecane; A=B(C6 H3 -3,5-Me2 )4 ) reacted with two equivalents of phenylsilane to give the bridging hexahydridosilicate complex [(Me4 TACD)2 Sr2 (thf)4 (µ-κ3 : κ3 -SiH6 )][A]2 (3 a). Rapid phenyl exchange between phenylsilane molecules is assumed to generate monosilane SiH4 that is trapped by two strontium hydride cations [(Me4 TACD)SrH(thf)x ]+ . Complex 3 a decomposed in THF at room temperature to give the terminal silanide complex [(Me4 TACD)Sr(SiH3 )(thf)2 ][A], with release of H2 . Upon reaction with a weak Brønsted acid, CO2 , and 1,3,5,7-cyclooctatetraene SiH4 was released. The reaction of a 1 : 2 mixture of cationic benzyl and neutral dibenzyl complex with phenylsilane gave the trinuclear silanide complex [(Me4 TACD)3 Sr3 (µ2 -H)3 (µ3 -SiH3 )2 ][A], while n OctSiH3 led to the trinuclear (n-octyl)pentahydridosilicate complex [(Me4 TACD)3 Sr3 (µ2 -H)3 (µ3 -SiH5 n Oct)][A].

Calcium Hydride Catalysts for Olefin Hydrofunctionalization: Ring-Size Effect of Macrocyclic Ligands on Activity.

The fifteen-membered NNNNN macrocycle Me5 PACP (Me5 PACP=1,4,7,10,13-pentamethyl-1,4,7,10,13-pentaazacyclopentadecane) stabilized the [CaH]+ fragment as a dimer with a distorted pentagonal bipyramidal coordination geometry at calcium. The hydride complex was prepared by protonolysis of calcium dibenzyl with the conjugate acid of Me5 PACP followed by hydrogenolysis or treating with n OctSiH3 of the intermediate calcium benzyl cation. The calcium hydride catalyzed the hydrogenation and hydrosilylation of unactivated olefins faster than the analogous calcium complex stabilized by the twelve-membered NNNN macrocycle Me4 TACD (Me4 TACD=1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane). Kinetic investigations indicate that higher catalytic efficiency for the Me5 PACP stabilized calcium hydride is due to easier dissociation of the dimer in solution when compared to the Me4 TACD analogue.

Deaggregation of Zinc Dihydride by Lewis Acids Including Carbon Dioxide in the Presence of Nitrogen Donors.

Thermally sensitive polymeric zinc dihydride [ZnH2]n can conveniently be prepared by the reaction of ZnEt2 with [AlH3(NEt3)]. When reacted with CO2 (1 bar) in the presence of chelating N-donor ligands Ln = N,N,N',N'-tetramethylethylenediamine (TMEDA), N,N,N',N'-tetramethyl-1,3-propanediamine (TMPDA), N,N,N',N″,N''-pentamethyldiethylenetriamine (PMDTA), and 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane (Me4TACD), insertion into the Zn-H bond readily occurred. Depending on the denticity n, formates [(Ln)Zn(OCHO)2] were isolated and structurally characterized, either as a molecule (Ln = TMEDA, TMPDA, PMDTA) or a charge-separated ion pair [(Ln)Zn(OCHO)][OCHO] (Ln = Me4TACD). The reaction of [ZnH2]n with the mild Lewis acid BPh3 in the presence of chelating N-donor ligands Ln gave a series of hydridotriphenylborates, either as a contact ion pair [(L2)Zn(H)(HBPh3)] (L2 = TMEDA, TMPDA) or a separated ion pair [(Ln)Zn(H)][HBPh3] (Ln = PMDTA, Me4TACD). In the crystal, the contact ion pair [(TMEDA)Zn(H)(HBPh3)] showed a bent Zn-H-B bridge indicative of a delocalized Zn-H-B interaction. In contrast, a linear Zn-H-B bridge for [(TMPDA)Zn(H)(HBPh3)] was observed, suggesting a contact ion pair. In THF solution, both complexes show an exchange with free BPh3 as well as [HBPh3]-. DFT calculations suggest the presence of [HBPh3]- anion with a highly polarized B-H bond that interacts with the Lewis acidic zinc hydride cation [(L2)Zn(H)]+. The hydridotriphenylborates [(Ln)Zn(H)(HBPh3)] underwent CO2 insertion to give (formato)zinc (formoxy)triphenylborate complexes [(Ln)Zn(OCHO)][(OCHO)BPh3] (Ln = TMPDA, PMDTA, Me4TACD). For Ln = TMEDA, a dinuclear complex [(Ln)2Zn2(µ-OCHO)3][(OCHO)BPh3] was isolated. Hydridotriphenylborates [(Ln)Zn(H)(HBPh3)] catalyzed the hydrosilylation of CO2 (1 bar) by nBuMe2SiH in THF at 70 °C to give formoxysilane and (methoxy)silane.

Reduced Arene Complexes of Hafnium Supported by a Triamidoamine Ligand.

A series of hafnium complexes with a reduced arene of the general formula [K(L)][Hf(Xy-N3 N)(arene)] (Xy-N3 N={(3,5-Me2 C6 H3 )NCH2 CH2 }3 N3- , L=THF, 18-crown-6; arene=C10 H8 2- , C14 H10 2- ) mimic the chemistry of hafnium in its formal oxidation state +II. All compounds were obtained upon reduction of the chlorido complex [HfCl(Xy-N3 N)(thf)] with two equivalents of potassium naphthalenide or anthracenide. The reducing nature and the basicity of the reduced anthracene ligand were explored in the reaction of benzonitrile and azobenzene, and by deprotonation of tert-butylacetylene, respectively. The reduction of benzonitrile provides an initial double nitrile insertion product under kinetic control that rearranges after extrusion of one of the inserted nitriles to a hafnium imido complex as the thermodynamic product. The reduction of azobenzene resulted in a diphenylhydrazido(2-) complex. Treatment of terminal alkynes with the anthracene or diphenylhydrazido(2-) complex led to the selective protonation of the corresponding dianionic ligand.

Reduced Arene Complexes of Scandium.

Alkali metal naphthalenide or anthracenide reacted with scandium(III) anilides [Sc(X){N(tBu)Xy}2 (thf)] (X=N(tBu)Xy (1); X=Cl (2); Xy=C6 H3 -3,5-Me2 ) to give scandium complexes [M(thf)n ][Sc{N(tBu)Xy}2 (RA)] (M=Li-K; n=1-6; RA=C10 H8 2- (3-Naph-K) and C14 H10 2- (3-Anth-M)) containing a reduced arene ligand. Single-crystal X-ray diffraction revealed the scandium(III) center bonded to the naphthalene dianion in a σ2 :π-coordination mode, whereas the anthracene dianion is symmetrically attached to the scandium(III) center in a σ2 -fashion. All compounds have been characterized by multinuclear, including 45 Sc NMR spectroscopy. Quantum chemical calculations of these intensely colored arene complexes confirm scandium to be in the oxidation state +3. The intense absorptions observed in the UV/Vis spectra are due to ligand-to-metal charge transfers. Whereas nitriles underwent C-C coupling reaction with the reduced arene ligand, the reaction with one equivalent of [NEt3 H][BPh4 ] led to the mono-protonation of the reduced arene ligand.

Alkali Metal Triphenyl- and Trihydridosilanides Stabilized by a Macrocyclic Polyamine Ligand.

Potassium silanide [KSiH3 ]∞ contains 4.2 wt % of hydrogen and has been intensely studied as hydrogen storage material. The macrocyclic ligand Me4 TACD (1,4,7,10-tetramethyl-1,4,7,10-tetraaminocyclododecane, L) stabilizes the full range of triphenylsilyl complexes [(L)MSiPh3 ]n (M=Li-Cs), which react with H2 or PhSiH3 to form molecular [(L)MSiH3 ]n that can be isolated in soluble form and fully characterized.

Reactivity of a Molecular Calcium Hydride Cation ([CaH]+) Supported by an NNNN Macrocycle.

The hydride ligand in the cationic calcium hydride supported by a NNNN-type macrocycle, [(Me4TACD)2Ca2(µ-H)2(THF)][BAr4]2 (1; Me4TACD = 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane; THF = tetrahydrofuran; BAr4 = B(C6H3-3,5-Me2)4), shows, in addition to its Brönsted basicity toward weak acids, a pronounced nucleophilicity resulting in nucleophilic substitution or insertion (addition) at a silicon or sp2 carbon center. Terminal acetylenes RC≡CH (R = SiMe3, cyclopropyl) as well as 1,4-diphenylbutadiene were deprotonated by 1 to give dinuclear complexes [(Me4TACD)2Ca2(µ-C≡CR)2][BAr4]2 (2a, R = SiMe3; 2b, R = cyclopropyl) and [(Me4TACD)2Ca2(µ2-η4-1,4-Ph2C4H2)][BAr4]2 (3) with H2 evolution. The addition reaction with BH3(THF) gave a tetrahydridoborate complex, [(Me4TACD)Ca(BH4)(THF)2][BAr4] (4), with κ2-H2BH2 coordination in the solid state, suggesting a pronounced Lewis acidic calcium center. The behavior resulting from both Lewis acidity and hydricity becomes apparent in the nucleophilic substitution of fluorobenzene by 1 to give benzene and the dimeric fluoride complex [(Me4TACD)2Ca2(µ-F)2(THF)][BAr4]2·2.5THF (5). Analogous nucleophilic substitution reaction is observed for heterofunctionalized organosilanes XSiR3 [X = I, N(SiHMe2)2, N3; R = Me3 or HMe2], which resulted in the formation of calcium complexes [(Me4TACD)Ca(X)(THF)n][BAr4] (6-8) containing an X ligand along with hydrosilane HSiR3. An insertion reaction by 1 was observed with CO2 and CO to give dinuclear formato complex [(Me4TACD)2Ca2(µ-OCHO)2][BAr4]2 (9) and cis-enediolato complex [(Me4TACD)2Ca2(µ-OCH═CHO)][BAr4]2·3.5THF (10), respectively. The latter is believed to have been formed as a result of the dimerization of an initially generated formyl or oxymethylene complex, [(Me4TACD)Ca(OCH)]+.

Regioselective Hydrosilylation of Olefins Catalyzed by a Molecular Calcium Hydride Cation.

Chemo- and regioselectivity are often difficult to control during olefin hydrosilylation catalyzed by d- and f-block metal complexes. The cationic hydride of calcium [CaH]+ stabilized by an NNNN macrocycle was found to catalyze the regioselective hydrosilylation of aliphatic olefins to give anti-Markovnikov products, while aryl-substituted olefins were hydrosilyated with Markovnikov regioselectivity. Ethylene was efficiently hydrosilylated by primary and secondary hydrosilanes to give di- and monoethylated silanes. Aliphatic hydrosilanes were preferred over other commonly employed hydrosilanes: Arylsilanes such as PhSiH3 underwent scrambling reactions promoted by the nucleophilic hydride, while alkoxy- and siloxy-substituted hydrosilanes gave isolable alkoxy and siloxy calcium derivatives.

Molecular Zinc Hydride Cations [ZnH]+ : Synthesis, Structure, and CO2 Hydrosilylation Catalysis.

Protonolysis of [ZnH2 ]n with the conjugated Brønsted acid of the bidentate diamine TMEDA (N,N,N',N'-tetramethylethane-1,2-diamine) and TEEDA (N,N,N',N'-tetraethylethane-1,2-diamine) gave the zinc hydride cation [(L2 )ZnH]+ , isolable either as the mononuclear THF adduct [(L2 )ZnH(thf)]+ [BArF 4 ]- (L2 =TMEDA; BArF 4 - =[B(3,5-(CF3 )2 -C6 H3 )4 ]- ) or as the dimer [{(L2 )Zn)}2 (µ-H)2 ]2+ [BArF 4 ]- 2 (L2 =TEEDA). In contrast to [ZnH2 ]n , the cationic zinc hydrides are thermally stable and soluble in THF. [(L2 )ZnH]+ was also shown to form di- and trinuclear adducts of the elusive neutral [(L2 )ZnH2 ]. All hydride-containing cations readily inserted CO2 to give the corresponding formate complexes. [(TMEDA)ZnH]+ [BArF 4 ]- catalyzed the hydrosilylation of CO2 with tertiary hydrosilanes to give stepwise formoxy silane, methyl formate, and methoxy silane. The unexpected formation of methyl formate was shown to result from the zinc-catalyzed transesterification of methoxy silane with formoxy silane, which was eventually converted into methoxy silane as well.

Titanium(IV) Cations with Trigonal Monopyramidal Geometry: Unusual Lewis Acids Supported by a Triaryl Triamidoamine Ligand.

Protonolysis of the titanium alkyl complex [Ti(CH2 SiMe3 )(Xy-N3 N)] (Xy-N3 N=[{(3,5-Me2 C6 H3 )NCH2 CH2 }3 N]3- ) supported by a triamidoamine ligand, with [NEt3 H][B(3,5-Cl2 C6 H3 )4 ] or [PhNMe2 H][B(C6 F5 )4 ] afforded the cations [Ti(Xy-N3 N)][A] (A- =[B(3,5-Cl2 C6 H3 )4 ]- (1[B(ArCl )4 ]; B(ArCl )4 =tetrakis(3,5-dichlorophenyl)borate); A- =[B(C6 F5 )4 ]- (1[B(ArF )4 ]; B(ArF )4 =tetrakis[3,5-bis(trifluoromethyl)phenyl]borate). These Lewis acidic cations were reacted with coordinating solvents to afford the cations [Ti(L)(Xy-N3 N)][B(C6 F5 )4 ] (2-L; L=Et2 O, pyridine and THF). XRD analysis revealed a trigonal monopyramidal (TMP) geometry for the tetracoordinate cations in 1[B(ArX )4 ] and trigonal bipyramidal (TBP) geometry for the pentacoordinate cations in 2-L. Variable-temperature NMR spectroscopy showed a dynamic equilibrium for 2-Et2 O in solution, involving the dissociation of Et2 O. Coordination to the titanium(IV) center activated the THF molecule, which, in the presence of NEt3 , underwent ring-opening to give the titanium alkoxide [Ti(O(CH2 )4 NEt3 )(Xy-N3 N)][B(3,5-Cl2 C6 H3 )4 ] (3). Hydride abstraction from Cß,eq of the triamidoamine ligand arm in [Ti(CH2 SiMe3 )(Xy-N3 N)] or [Ti(NMe2 )(Xy-N3 N)] with [Ph3 C][B(3,5-Cl2 C6 H3 )4 ] led to the diamidoamine-imine complex [Ti(R){(Xy-N=CHCH2 )(Xy-NCH2 CH2 )2 N}][B(3,5-Cl2 C6 H3 )4 ] (R=CH2 SiMe3 (4 a); R=NMe2 (4 b)). Hydride addition to 4 b with [Li(THF)][HBPh3 ] gave [Ti(NMe2 )(Xy-N3 N)], whereas KH deprotonated further to give [Ti(NMe2 ){(Xy-NCH=CH)(Xy-NCH2 CH2 )2 N}] (5). XRD on single crystals of 3 and 4 b confirmed the proposed structures.

A Masked Cuprous Hydride as a Catalyst for Carbonyl Hydrosilylation in Aqueous Solutions.

Redox-unstable cuprous hydridotriphenylborate was isolated as an N-heterocyclic carbene adduct [(IPr)Cu(HBPh3 )] (IPr=1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) with good thermal stability. Although this compound displays a contact ion-pair structure, CuI H-like catalytic activity was envisaged in carbonyl hydrosilylation. Sufficient moisture stability allowed the catalysis in aqueous/organic media. Mechanistic study further showed that a phenyl group on the borate anion is abstracted by [(IPr)Cu]+ to give the cationic organocopper complex [(IPr)2 Cu2 (µ-Ph)][BPh4 ].

Titanium Carbene Complexes Stabilized by Alkali Metal Amides.

Facile α-H elimination from tetrakis(trimethylsilylmethyl)titanium precursors to give adducts of (alkylidene)bis(alkyl)titanium complexes is induced by light alkali metal amides of the NNNN-type macrocyclic anionic ligand Me3 TACD [(Me3 TACD)H=1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane]. In the crystal, the alkali metal interacts with the carbene carbon atom or with the CH2 group of the trimethylsilymethyl ligand. The nucleophilic character of the carbene carbon atom was shown by the reaction with benzophenone and terminal acetylenes.

The Nature of the Heavy Alkaline Earth Metal-Hydrogen Bond: Synthesis, Structure, and Reactivity of a Cationic Strontium Hydride Cluster.

The molecular strontium hydride [(Me3TACD)3Sr3(µ3-H)2][SiPh3] (2) was isolated as the dark red benzene solvate 2·C6H6 in 69% yield from the reaction of [Sr(SiPh3)2(thf)3] (1') with (Me3TACD)H (1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane). This reaction can be considered as a redox process, with the Brønsted acidic amine proton in (Me3TACD)H transformed into the hydride by the anion [SiPh3]-. Trace amounts of water resulted in the formation of [(Me3TACD)3Sr3(µ3-H)(µ3-OH)][SiPh3] (2*), which cocrystallized with 2. Single-crystal X-ray diffraction of 2 revealed a substitutional disorder of a bridging hydride with a hydroxide ligand. Hydride complex 2 was also obtained by hydrogenolysis of [(Me3TACD)Sr(SiPh3)] (3), although pure 3 proved difficult to isolate. In the presence of a 2-fold excess of (Me3TACD)H, the reaction with disilyl 1' gave [(Me3TACD)SiPh3] (4). Complex 2 underwent facile H/D exchange with D2 (1 bar), with the anion [SiPh3]- decomposing concurrently. In the reaction of 2 with 1,1-diphenylethylene (DPE), the anion [SiPh3]- was added to the C═C bond in DPE to give [(Me3TACD)3Sr3H2][Ph2CCH2SiPh3] (5), whereas the cationic cluster [(Me3TACD)3Sr3H2]+ remained unchanged. 9-Fluorenone underwent one-electron reduction with 2 to give the paramagnetic ketyl complex [{(Me3TACD)H}Sr(OC13H8•)2(thf)2] (6). These strontium compounds are structurally similar to the lighter calcium congeners, but more reactive, in particular with regard to fast H/D exchange and [SiPh3]- anion decomposition. DFT studies on the cationic hydride clusters suggest a more pronounced covalent character for strontium compared to calcium. Disilyl 1, strontium diketyl 6, and the calcium congener of 6, [{(Me3TACD)H}Ca(OC13H8·)2] (10), were also characterized by X-ray diffraction.